Resinous condensation product from dihydroxydiphenylethane and reactive methylene bodies and process of making same



the advanta 45 of formaldehyde or acetone, s'u

Patented 2, 1927.

"UNITED STATES "-IP'ATE'NT OFFICE.

LEO E. IBAEKELAND, OI YONKEBS, N YORK, ASSIGNOR '10 BAKELITE CORPORATION, 01' NEW YORK, N. Y., A CORPORATION OF DELAWARE.

BESINOUS CONDENSATION PRODUCT FROM DIHYDBOZYDIPHENYLETHANE AND BE- ACTIVE METHYLENE BODIES AND PROCESS OF MAKING SAME.

Io Drawing.

This invention relates to a novel process whereby resinous phenolic condensation products similar to or identical with certain known substances of this type are sim- 5 ly and economically prepared from dihyroxydiphenylethane, CH CH (G l-LOH) also cal ed p-diphenylolethane or eth hdenediphenol 1, 1. (Compare Beilstein, buch der Organischen Chemie, Vol. II, 1 1896, page 994.)

s-is now well understood, phenolic condensation products of the resinous type may be directly prepared by reaction between-phenols and formaldehyde or equivalent bodies having a mobile methylene group. Similar bodies are also prepared by reaction involving phenols and acetalde hyde, for example bythe method described in the copending U. S. application of Backeland and Gotthelf, Serial No. 346,104, filed December 19, 1919. According to the pres-, ent invention such resinous phenolic condensation products are repared directly by condensation of dihy roxydiphenylet ans 2 with a relatively small proportion of para- -form, hexamethylenetetramine, or equivalent substance havin a reactive or mobile methylene group. Di ydroxydiphenylethane may be slmply prepared in the form of crystals, for example by reacting on acetal dehyde with phenol in presence of hydrochloric acid, and allowing the mixture to stand in the cold until the crystallization is complete; and the present process presents the lmportant advantage that the principal raw materials, phenol and acetalde' yde, are both readily prepared by synthetic methods from raw materials of which the supplies are practically unlimited. It possesses also that the dihydroxydiphenylethane is easily prepared in relatively pure state and at a comparatively low cost; The fact that the process does not involve the .-direct or indirect use in large proportions stances of which the available supply andthe market rice have been subject/to wide fluctuations 1n the ast is a commercial consideration of the liighest. importance. Furthermore,

and-

Application filed June 30, 1922. Serial No. 572,082.

the rocess permits a more direct .control of t e reaction, which approaches more closely the conditions of theoretical simplicmethyl'enetetramine; They are adaptable to the numerous technical uses which have been found for this class of product, now Widely known as phenolic condensation products, synthetic resins, or under various manufacturers tradenames.

According to the method of preparation as well as the proportions of the reacting substances, I obtain resinous or resinoid bodies varying widely in their characteristics and properties, such as fusibility, solubility, and general resistant quality toward chemical or physical influences, ranging from the fusible resins or so-called shellac substitutes on the one hand, through intermediate grades, to the type of infusible or insoluble resinoid bodies of great mechanical strength and resistance on the other hand.

These products in' their various forms, and either before or after the com letion of the reaction, may be incorporate brous materials or other suitable fillers, or withsolid solvents or plasticizing agents of any kind; orthey may while in the soluble potentially reactive state be employed in the manufacture of varnishes, la uers, ce-

mnts or solutions of any kind. ey may be employed in the potentially reactive state for the lmpregnation of porous materials,

either organic or inorganic; or used in the manufacture of impregnated papers or fabrics, cardboards, laminated products and the like, by absorbing them. in or inter-posing them between layers of paper, felt or" woven fabric, and then subjecting the prod- Example I.

100 parts of weight of dihydroxydiphenylethane are heated with ten partsof paraform, first at about 180 C. and later I at about 200 C. until a transparent, fusible resinous mass is obtained, which solidifies on cooling to a brittle resin, usually of a light brown color and soluble in acetone and some other organic solvents. The general properties of this substance are similar to those of the material heretofore designated Novolak. (SeeBaekeland, Journal of In-.,

dust rial and Engineering Chemistry, Vol. 'I, No. 8 Aug. 1909). .In case a higher degree of fusibility or solubility is desired in the resin the roportion of paraform may be somewhat reduced.

E wampl e' I I 100 parts b weight of the resin prepared according to xample I are mixed with a proximatel 10 parts of paraform and su jected to fhrther heating until a hard, in-' fusible mass results. Thistheating is preferably carried out under external pressure to insure homogeneity in the mass: and as is now well understood in this art, the heating is generally applied simultaneously with the shaping of the article molded article, laminated plate, etc.) in a ydraul-ic press having steam-heated platens, the heating being continued until the transformation-of the shaped article into the hard and infusible state has been accomplished. If the heating be carried out in a closed vessel, under pressure and without admixture'of filler with the resin, the latter appears as a transparent or translucent, hard massfinsoluble or incompletely soluble in acetone.

, Example II I The process is carried out as in Example II except that about 12 parts, of'hexamethylenetetramine are substituted for the 10 parts of paraform used for the transformation of the soluble and fusible resin. The resulting product is essentially similar to that of Example-II, but exhibits a somewhat increased tendency to swell and disintegrate in acetone" without completely dissolving therein.

Example IV.

tained.

" Example Dihydroxydiphenylethane is heated with paraform or hexamethylenetetramine under conditions substantially as described in the preceding examples, but with such increased proportions of the methylene=containing agent as to produce directly the harden' lIlfllSlbfiOd which, according to Examples II, III, and V, is repared in' a two-stage operation. This e ect may be obtained by the use of 20 parts or upward of paraform, and corresponding proportions of. hexamethylenetetrami-ne. a

While in the foregoing examples I have referred to dihydroxydiphenylethane, it is to be understood that my invention contemplates the partial substitution for this body of other phenolic bodies, with modifying effects upon the hardness, color, plasticity, solublity and general resistant qualities of the product. 11 the several cases the proportions of the reacting bodies may be varied as desired to secure graded technlcal efiects. The paraform and hexamethylenetetramine may be used in admixture with each other, or replaced, wholly orvin art by other bodies containing reactive met ylene groups and capable of roducin similar or equivalent technical eflgcts' or y other suitable aldehyde amines or hardening agents.

I claim: a

1. Process of preparing a resinuous con densation product comprising reactin with a hardening agent upon dihydroxydip enylethane until a resinous condensation prodnot is formed.

2. Process of preparing a resinuous condensation product comprlsing reacting with a body containin a mobile methylene group upon dihydroxy iphenylethaneuntil a resinous condensation product is formed.

3. Process of preparing an infusible condensation product comprlsing reacting with a body containin a mobile methylene group upon dihydroxyd iphenylethane, the reagents proportioned to yield a fusible resin; and transforming said resin into an infusible body by reactin thereon with a'further proportiomof a met ylene-containing agent.

- 4. The hereindescribed-resin-like reaction product of dihydroxydiphenylethane and a bodycontaining a mobile methylene group. p 5. A new composition of matter compris ing a resinous condensation product of di- 7. A potentially reactive composition com- A hydroxydiphenylethane and a hardening Erising a resinous reaction roduct of diagent. ydroxydiphenyletha-ne,' an hexamethyl- 10 6. A potentially reactive composition enetetramine. 5 comprising a resinous reaction product oi In testimony whereof,I aflix my signature.

dihydroxydiphenylethane, and a. hardening agent therefor. LEO H. BAEKELAND. 

